Process for the preparation of alcohols and diols

Abstract

A process is described for reactivating an at least partially deactivated copper-containing ester hydrogenation catalyst which has undergone deactivation through use in hydrogenation of an unsaturated organic compound selected from esters of C 8 to C 22 monocarboxylic acids, diesters of dicarboxylic acids, and lactones, to yield a corresponding hydroxylic compound selected from alcohols and diols which comprises contacting the at least partially deactivated copper-containing catalyst at an effective reactivation temperature and for an effective period of time with a stream of hydrogen-containing gas which is substantially free from the unsaturated organic compound thereby to reactivate the at least partially deactivated copper-containing catalyst.

We claim: 
     
       1. A process for the production of alcohols and diols by hydrogenation of a corresponding unsaturated organic compound selected from esters, diesters and lactones which comprises: (a) providing a hydrogenation zone containing a charge of a granular copper-containing ester hydrogenation catalyst;   (b) supplying to the hydrogenation zone, in a first phase of operation, a vaporous feed stream comprising a hydrogen-containing gas and an unsaturated organic compound selected from C 1  to C 4  alkyl esters of C 8  to C 22  alkylcarboxylic acids, di-(C 1  to C 4 ) diesters of C 4  to C 16  dicarboxylic acids, gamma-butyrolactone and epsilon-caprolactone;   (c) maintaining the hydrogenation zone, in the first phase of operation, at a temperature in the range of from about 150° C. to about 350° C. and a pressure in the range of from about 150 psia up to about 2000 psia;   (d) recovering from the hydrogenation zone, in the first phase of operation, a reaction product stream comprising the alcohol or diol;   (e) supplying to the hydrogenation zone, in a second phase of operation, a stream of hydrogen-containing gas which is substantially free from the unsaturated organic compound at an effective reactivation temperature and for an effective period of time thereby to reactivate the charge of copper-containing ester hydrogenation catalyst therein.   
     
     
       2. A process according to claim 1, in which the stream of hydrogen-containing gas of step (e) comprises a hot stream of recycle and make-up gas. 
     
     
       3. A process according to claim 1, in which the vaporous hydrogen-containing stream of the unsaturated organic compound of step (b) is substantially saturated with the unsaturated organic compound. 
     
     
       4. A process according to claim 3, in which the vaporous feed stream of step (b) is at a feed temperature at least about 5° C. above its dew point. 
     
     
       5. A process according to claim 1, in which the temperature and pressure of step (c) comprise a temperature of from about 150° C. to about 300° C. and a pressure of from about 450 psia (about 31.03 bar) to about 1000 psia (about 68.95 bar) and the copper containing hydrogenation catalyst is reduced copper chromite catalyst wherein the Cu:Cr weight ratio is from about 0.1:1 to about 4:1; reduced, copper chromite catalyst wherein the Cu:Cr weight ratio is from about 0.1:1 to about 4:1 promoted with from about 0.1% by weight up to 15% by weight of barium, manganese or a mixture of barium and manganese; or reduced manganese promoted copper catalyst wherein the Cu:Mn weight ratio is from about 2:1 to about 10:1. 
     
     
       6. A process according to claim 5, in which the unsaturated organic compound comprises dimethyl 1,4-cyclohexanedicarboxylate and in which the hydrogenated product comprises 1,4-cyclohexanedimethanol. 
     
     
       7. A process according to claim 5, in which the unsaturated organic compound comprises dimethyl 1,2-cyclohexanedicarboxylate and in which the hydrogenated product comprises 1,2-cyclohexanedimethanol. 
     
     
       8. A process according to claim 5, in which the unsaturated organic compound comprises dimethyl 1,3-cyclohexanedicarboxylate and in which the hydrogenated product comprises 1,3-cyclohexanedimethanol. 
     
     
       9. A process according to claim 5, in which the unsaturated organic compound comprises an ester selected from dimethyl and diethyl maleate and in which the hydrogenated product comprises butane-1,4-diol. 
     
     
       10. A process according to claim 5, in which the unsaturated organic compound comprises gamma-butyrolactone and the hydroxy compound comprises butane-1,4-diol. 
     
     
       11. A process according to claim 5, in which the period used for reactivation ranges from about 1 hour up to about 24 hour. 
     
     
       12. A process according to claim 5, in which the reactivation temperature of step (e) lies in the range of from about 150° C. to about 350° C. and is from about 50° C. less than to about 50° C. more than the feed temperature of the vaporous feed stream to the hydrogenation zone. 
     
     
       13. A process according to claim 5, in which the copper-containing catalyst is selected from reduced copper chromite, reduced promoted copper chromite, and manganese promoted copper catalysts. 
     
     
       14. A process for reactivating an at least partially deactivated copper-containing ester hydrogenation catalyst which has undergone deactivation through use in hydrogenation of an unsaturated organic compound selected from esters of C 8  to C 22  monocarboxylic acids, diesters of dicarboxylic acids, and lactones, to yield a corresponding hydroxylic compound selected from alcohols and diols which comprises contacting the at least partially deactivated copper-containing catalyst at an effective reactivation temperature and for an effective period of time with a stream of hydrogen-containing gas which is substantially free from the unsaturated organic compound thereby to reactivate the at least partially deactivated copper-containing catalyst. 
     
     
       15. A process for reactivating an at least partially deactivated copper-containing ester hydrogenation catalyst which has undergone deactivation through use in hydrogenation of an unsaturated organic compound selected from C 1  to C 4  alkyl esters of C 8  to C 22  monocarboxylic acids, di-(C 1  to C 4 ) diesters of C 4  to C 16  dicarboxylic acids, gamma-butyrolactone and epsilon-caprolactone, to yield a corresponding alcohol or diol which comprises contacting the at least partially deactivated copper-containing catalyst at an effective reactivation temperature and for an effective period of time with a stream of hydrogen-containing gas which is substantially free from the unsaturated organic compound thereby to reactivate the at least partially deactivated copper-containing catalyst. 
     
     
       16. A process according to claim 15 for reactivating an at least partially deactivated copper-containing ester hydrogenation catalyst wherein the copper containing hydrogenation catalyst is reduced copper chromite catalyst wherein the Cu:Cr weight ratio is from about 0.1:1 to about 4:1; reduced, copper chromite catalyst wherein the Cu:Cr weight ratio is from about 0.1:1 to about 4:1 promoted with from about 0.1% by weight up to 15% by weight of barium, manganese or a mixture of barium and manganese; or reduced manganese promoted copper catalyst wherein the Cu:Mn weight ratio is from about 2:1 to about 10:1.